Quaternary methine dyes for acrylic fibers



United States Patent 3,247,215 QUATERNARY METHINE EYES FOR ARYLliCFIBERS John G. Fisher, David 3. Wallace, and James M. Straley,

Kingsport, Tenn, assignors to Eastman Kodak Company, Rochester, N.Y., acorporation of New Jersey No Drawing. Filed Sept. 6, 1963, Ser. No.306,990 Claims. (01. 260-2943) This invention relates to new methinecompounds and particularly to new quaternary compounds especially usefulin the art of dyeing or coloring.

This application is a continuation-in-part of our US. patent applicationSerial No. 125,343, filed July 20, 1961, now U.S. Patent No. 3,141,018.

In our parent application are disclosed methine compounds having theformula:

R2 I X wherein R and R each represents an alkyl radical having 1 to 4carbon atoms, R represents an alkyl radical having 1 to 4 carbon atomsor a fi-cyanoethyl group, Y represents an alkylene radical having 2 to 4carbon atoms, X represents a cyano group, a COOCH CH CN group or a COORgroup, wherein R represents an alkyl radical having 1 to 4 carbon atoms,Z represents a hydrogen atom or a methyl radical and whereincollectively represents a morpholinyl radical or a piperidyl radical,and the quaternary ammonium salts of said methine compounds.

The quaternary compounds of the present invention include tetraalkylquaternary ammonium compounds and quaternary ammonium compounds in whichthe quaternary nitrogen atom is a part of a ring system having thegeneral formula.

wherein R: an alkyl radical including unsubstituted alkyl, preferablylower alkyl of 1 to 4 carbon atoms such as methyl, ethyl, propyl,isopropyl, butyl, and substituted allcyl, preferably substituted loweralkyl such as alkoxyalkyl e.g. methoxyethyl, ethoxypropyl, aryloxyalkyle.g. phenoxyethyl, arylalkyl e.g. benzyl, cyanoalkyl e.g.B-cyanoethyhhaloalkyl e.g. [i-choroethyl.

R R and R each: a lower alkyl radical including unsubstituted loweralkyl of 1 to 4 carbon atoms and substituted lower alkyl such as benzyl,cyanoethyl etc., or R R and R together with the nitrogen atom (N+) towhich they are attached from unsubstituted or substituted pyridinium,quinolinium, morpholinium or piperidinium radicals such as pyridinium,Z-pic-olinium, 2- benzylpyridinium, 2,4-dimethylpyridinium,2,6-dimethylpyridinium, 2-n1ethyl-S-ethylpyridinium,2,4,6-trimetl1ylpyridinium, 4-benzylpyridinium, 3 -methylpyridiniumquinolinium and 3-benzyl-, 2,4-diethoxy-, 6-methoxy-, 3- ethyl-,3-ethoxy-, 2-ethyl-, 3-methyl-, 4-butoxy, 4-phenoxyandS-phenyl-quinolinium radicals; piperidinium and 2- benzyb,2-cyclohexyl-, 4,4-dimethyl-3-phenyl-, 3,4-diphenyl-, 4-isopropyl-,4-methoxy-, 3-methyl-, 4-methyl-, 3- phenyland 4-phenyl-piperidiniumradicals; morpholinium, 4-benzyl, 2,6-dimethyl-, 4-phenyl-, 4methyl, 4-ethoxymethyl-, 4-propylmorpholinium radicals,

3 ,24 7 ,2 l5 Patented Apr. 1 9, 1 966 ice Y=lower alkylene of l to 4carbon atoms such as methylene, ethylene, propylene, butylene,

R =a p-phenylene radical including unsubstituted pphenylene andsubstituted p-phenylene such as lower alkyl-p-phenylene e.g. 2-rnethyl-,3-butyl-, 3-methyl-pphenylene; lower alkoxy-p-phenylene e.g.Z-methoxyand 3-methoxy-p-phenylene, etc.,

X=cyano, COOCH CH CN, lower COOalkyl, CONH or lower CON(alkyl) Z=ianranion or acid radical such as halogen, eg I, Cl, p-toluene sulfonate,methosulfate, and other anions derived from well-known quaternizingagents,

A group of the quaternary compounds particularly efiicacious as dyes fortextile materials have the formula ON in which Py is a substituted orunsubstituted N-pyridinium radical such as given above, Y is loweralkylene especially ethylene, R is lower alkyl especially ethyl orpropyl, R is p-phenylene especially Z-methyl-p-phenylenc, X is CONH CNor COOCH and Z is an acid anion derived from a quaternizing agent.

The quaternary methine compounds of our invention are valuable dyestuffsfor various synthetic textile materials. The quaternary methinecompounds dye polyacrylonitrile and modified polyacrylonitrile textilematerials fast, bright yellow shades. The quaternary methine compoundshave good afiinity for the aforesaid textile materials and yield bri htyellow dyeings thereon which have good fastness to light, gas,sublimation and wet processing. Wet processing includes, for example,washing, perspiration, wet ironing and wet sublimation.

Verel modacrylic, Orlon 42 acrylic, Dacron and Kodel polyester textilematerials are illustrative of materials that can be dyed with the newmethine compounds of our invention. Cellulose esters that can be dyedinclude, for example, cellulose acetate, cellulose propionate, cellulosebutyrate, cellulose acetate-propionate and cellulose acetate-butyrate.In particular, the quaternary methine compounds exhibit substantiallybetter fastness to sublimation than do the corresponding non-quaternarymethine compounds of our parent invention. For example, the quaternarycompound of Example 3 below has better sublimation fastness than eitherthe corresponding nonquaternized compound of Example 2 or thenon-quaternized compound of Example 4.

The tetraalkyl quaternary ammonium methine compounds can be prepared asdescribed in our parent invention by quaternization of thenon-quaternary compounds of formula R; X wherein R, R R R X and Y havethe meaning given above.

Quaternization may be carried out in an inert solvent using the knownquaternizing agents. A dialkyl sulfate, an alkyl chloride, an alkylbromide, an alkyl iodide, an aralkyl chloride, an ara-lkyl bromide or analkyl ester of paratoluene sulfonic acid, for example, can be employed.Specific quaternize agents include, for example, dimethyl sulfate,diethyl sulfate, dipr-opyl sulfate, dibutyl sulfate, ethyl bromide,ethyl chloride, methyl iodide, ethyl iodide, n-butyl iodide, lauryliodide, benzyl chloride, benzyl bromide, methyl ptoluene sulfonate,ethyl p-toluene sulfonate, n-pr-opyl ptoluene sulfonate and n-butylp-toluene sulfonate. Methine compounds useful as textile dyes areobtained regardless of the type of quarternizing agent used. Inertsolvents that can be employed in the quaternization reaction include,for example, dimethyl formamide, acetone, ethylene glycol monoethylether, isopropanol, n-butanol, chlorobenzene and nitrobenzene.

The non-quaternary methine compounds are prepared as described in ourparent application by reacting the adehydes l N--Y1iIB oH R: with activemethylene compounds having the formula NCCH X, such as malononitrile.

Alternately, the tetraalkyl quaternary compounds can be made byquaternizing the aldehydes and condensing the product with the activemethylene compound NCCH X.

Similarly, the heterocyclic quaternary ammonium methine compounds can beobtained as described in the examples below by reacting the aldehydes RCl-YI IR4CHO with pyridine, quinoline, piperidine or morpholine, thenreacting with NCCH X or the methine dye R CN CIYI IR4CH=C IX may betreated with pyridine, quinoline, and their derivatives, etc.

Malononitrile, cyanoacetarnide, B-cyanoethyl cyanoacetate, isopropylcyanoacetate, n-butyl cyanoacetate and tertiarybutyl cyanoacetate areillustrative of the active methylene compounds used in the preparationof the new methine compounds of our invention.

p-(N-ethyl-N-diethylaminoethylamino)-2-methyl benzaldehyde,

p-(N-n-propyl-N-diethylaminoethylamino) -2-methylbenzaldehyde,

p- N-n-butyl-N-die thylaminoethyl amino -2-methyl benzaldehyde,

p-(N-ethyl-N-di-n-propylaminoethylamino)-2-methylbenzaldehyde,

p-(N-ethyl-N-di-n-butylaminoethylamino -2-methylbenzaldehyde,

p- (N-ethyl-N-B-morpholinoethylamino -2-methylbenzaldehyde,

p-(N-ethyl-N-v-morpholinopropylamino) -2-methylbenzaldehyde,

i p-(N-ethyl-N-delta-morpholinobutylamino)-2-methylbenzaldehyde,p-(N-ethyl-n-fl-piperidinoethylamino)-2-methlybenzal dehyde, p-(N-ethyl-N-y-piperidinopropylamino-2-methylbenzaldehyde,p-(N-ethyl-N-v-diethylaminopropylamino)-2-methylbenzaldehyde,p-(N-ethyl-N-delta-diethylaminobutylamino)-2-methylbenzaldehyde, and-p-(N-ethyl-N-delta-piperdino'butylamino)-2-methylbenzaldehyde,p-(N-fi-chloroethyl-N-ethylamino)-o-tolyl aldehyde, andp-(N-[i-chlor-oethyl-N-butyl)benzaldehyde are representative of thebenzaldehyde compounds used for preparation of our new quaternizedmethine compounds. I

The following examples illustrate the compounds of our invention andtheir manner of preparation.

EXAMPLE 1 Aldehyde preparation To a solution of 26.2 grams ofN-n-butyl-N-fi-diethylaminoethyl-m-toluidine in 20 cc. ofdimethylformamide there were added slowly with stirring at 10-20 C. 11cc. of POCl The reaction mixture resulting was heated on the steam bathfor 1.5 hours. After cooling, the reaction mixture was drowned in 20volumes of water, made slightly basic with NaOH and extracted with cc.of CHCl The extract was evaporated to dryness. p-(N-nbutyl NB-diethylaminoethylamino)-2-methylbenzaldehyde was recovered as a stickyresidue and was used as such.

EXAMPLE 2 A solution of 29 grams of the product of Example 1, 6.6 gramsof malononitrile and 1 cc. of piperidine in 100 cc. of alcohol wascooled to 10 C. Yellow crystals of thedesired product precipitated andwere recovered by filtration, washed with cold methyl alcohol andair-dried.

The product obtained has the formula:

C4Ha n I f (CzHa)2NOH2CH2-NCH=C (IJH: \CN

and melts at 77-78" C.

EXAMPLE 3 Quaternizalion Three grams of the product of Example 2, 0.5cc. of dimethylsulfate and 5 cc. of dry chlorobenzene were stirredtogether at 40 50 C. After about an hour the reaction mixture was cooledto room temperature, the oil formed solidifying. The reaction productwas recovered by filtration, washed with ether and dried in a vacuumdesiccator. A quaternary ammonium salt form of the methine compound ofExample 2 was obtained. It is water-soluble and dyes Orlon and Vereltextile materials fast yellow shades. The dye has the formula O4H0 C Nand possesses excellent sublimation fastness compared to thenon-quaternary compounds of Examples 2 and 4 which exhibit appreciablesublimation.

EXAMPLE 4 A solution of 23.4 grams of4-N-ethyl-N-p-dimethylaminoethylamino)-2-methylbenzaldehyde, 6.6 gramsof .malononitrile and 1 cc. of piperidine in 100 cc. of alcohol wasrefluxed for 1 hour. The reaction mixture resulting was cooled to 10 C.Yellow crystals of the desired product precipitated and were recoveredby filtration, washed with cold methyl alcohol and air-dried. Themethine compound thus obtained dyes Orlon and Verel textile materialsfast, bright yellow shades.

EXAMPLE 5 Quaternization 1 gram of the product of Example 4 was heatedon the steam bath for 2 hours with 5 cc. of dimethyl sulfate. Aftercooling, the reaction mixture was diluted with 5 volumes of ether andthe product which precipitated was recovered by filtration, washed withether and dried. A quaternary ammonium salt form of the methine compoundof Example 4 was obtained. It is water-soluble and dyes Verel and Orlontextile materials fast greenishyellow shades.

EXAMPLE 6 Thirty grams of4-(N-ethyl-N-y-morpholinopropylamino)-2-methylbenzaldehyde, 9.9 grams ofmethyl cyanoacetate, 1 cc. of piperidine and 100 cc. of alcohol wererefluxed together for 1 hour. The reaction mixture was then diluted withhot water to incipient crystallization and cooled to room temperaturewhile stirring. The product which precipitated was recovered byfiltration, washed with water and air-dried. The product quaternizedwith dimethylsulfate as in Example 3, dyes acrylic and modacrylic fibersfast yellow shades.

EXAMPLE 7 The process of Example 1 was carried out using 28.2 g. of 4 Nethyl-N-(N,N'-di-fl-cyanoethylamino)ethyl-mtoluidine. 15.6 g. (0.05 m.)of the product were treated with 3.3 g. of m'alononitrile and 5 drops ofpiperidine in 50 cc. of alcohol as in Example 2.

EXAMPLE 8 5 g. of the product of Example 7, 5 g. of methyl iodide and 50cc. of ether were mixed and allowed to stand at room temperature for 72hours. The solid was filtered off, washed and dried. It dissolves inwarm water and imparts fast greenish-yellow shades to Orlon and Vereltextiles.

EXAMPLE 9 The process of Example 2 was used with 25.8 g. of 4-(N-ethyl-N-B-diethylaminoethyl) -2-methylbenzaldehyde.

EXAMPLE 10 1 g. of the dye of Example 9, 1 g. of ethylp-toluenesulfonate and 7 cc. of dry benzene were stirred at C. for 2hours. The yellow solid was filtered off, washed with ether andair-dried. The product dyes acrylic fibers in bright greenish-yellowshades.

EXAMPLE 11 Aldehyde preparation 200 ml. of phosphorous oxy chloride wasadded over a four hour period of a solution of 179 g. ofN,B-hydroxyethyl-N-ethyl-m-toluidine in 90 ml. of dimethylformamide at atemperature of 25-90 C. After heating the reaction mixture on the steambath for two hours it was drowned in 6 l. of water and ice. Theresulting solid was filtered off and washed with 8 1. of water. Theyield of p-(N,B- chloroethyl-N-ethylamino)-o-t0lyl aldehyde was 179 g.It had a melting point of 46 to 47 C.

EXAMPLE 12 4.5 g. of the aldehyde of Example 11 was dissolved in 20 ml.of pyridine. The reaction solution was heated at reflux for 45 hrs.,cooled slightly, 1.32 g. malononitrile and 2 drops of piperidine addedand then reflux continued for 1 hr. The excess pyridine was removed bydistillation in vacuo and the residue dissolved in 200 ml. of water,filtered from any insoluble material and the dye precipitated byaddition of an aqueous solution of NaCl and ZnCl There is obtained thezinc chloride salt of the methine compound:

The product dyes Orlon acrylic fibers and Verel modacrylic fibers fastyellow shades.

EXAMPLE 13 The use of cyanoacetamide for malononitrile in the process ofExample 12 yields a quaternary dye in which the =C(CN) group of theExample 12 dye is replaced by =C(CN)CONH The product dyes Orlon acrylicfibers and Verel modacrylic fibers fast yellow shades.

EXAMPLE 14 The use of methylcyanoacetate for malononitrile in theprocess of Example 12 yields a dye in which the =C(CN) group of theExample 12 dye is replaced by -=C(CN)COOCH Tne product dyes Orlonacrylic fibers and Verel modacrylic fibers fast yellow shades.

EXAMPLE 15 The process of Example 12 is carried out using p-(N,[i-chloroethyl-N-butylamino)benzaldehyde in place of p- (N,;@chloroethylamino) o tolyl aldehyde. A yellow methine dye is obtained inwhich the CH CH group of the Example 12 dye is replaced by CH (CH Theproduct dyes Orlon acrylic fibers and Verel modacrylic fibers fastyellow shades.

EXAMPLE 16 4.5 g. of p-(N,/8-chloroethyl-N-ethylamino)-o-tolyl aldehydewas dissolved in 25 ml. or" quinoline. The reaction solution was heatedat C. for 24 hr., cooled slightly and 1.32 g. of malononitrile and 2drops of piperidine were added. After heating for /2 hr. on the steambath, the reaction mixture was drowned in dilute hydrochloric acid. Itwas filtered from any water insoluble material and the yellow dyeprecipitated by addition of NaI. The resulting dye has the structure ofExample 12 except that the N-pyridinium group is replaced by the N-quinolinium group. The product dyes Orlon acrylic fibers and Verelmodacrylic fibers fast yellow shades.

EXAMPLE 17 The use of fl-picoline in the process of Example 16 gives adye of structure as in Example 12 except that the Npyridinium group isreplaced by the N-,B-picolinium group. The product dyes Orlon acrylicfibers and Verel modacrylic fibers fast yellow shades.

EXAMPLE 17A 4.5 g. of the aldehyde of Example 1.1 and 1.32 g. ofmalononitrile were heated at reflux in 20 cc. of ethanol containing 2drops of piperidine. After one hour the mix was cooled and the productisolated by filtration. The dried solid was dissolved in 20 cc. of2-.picoline and heated at ll5l20 C. for 45 hours. The excess solvent wasremoved by distillation in vacuo and residue dissolved in 200 cc. ofwater. After filtration NaCl and ZnCl were added, precipitating the ZnClsalt of the dye.

CHgCHz The dyes described in the following table are pre- ExampleRzRgRaN R x R4 Y z is minimum-.. 02m CN 0,114 G1 19 d c2115 ON 1 1 02m01 B-Picolinium CzHs ON Oil-I4 1 21.; Quinolinium c2115 COOI-Ia c2114 0122 fl-Pic0linium 0,11, COzCHa. 0,114 1 23 Pyridinium 02m CO2CH(CH3)1 .Q.c2114 01 24 do 0,11, co,c1I2oHz00I-n- Czlh o1 25 do 0,115CO2C1'I2CH(CII3)2- Q- 0,11. 01

err;

26 do our COgCHgCHzON 0,11, 01

Other substituted anilines containing the radical wherein:

and which may be used to prepare the quaternary methine compounds aredisclosed in Example 14 of our parent application e.g. N isopropyl Npiperidinoethyl mtoluidine, which are converted to the aldehydes whichare then quaternized and the methine compounds prepared therefrom asdescribed.

The dyeing of acrylic fibers with the dyes such as described in Example3 can be carried out as follows:

16.7 mg. of the dye of Example 3 was added to 200 cc. of hot water. Fivecc. of 10% formic acid was added followed by 5 g. of Orlon 42 acrylicfabric. The bath was brought to the boil and held one hour. The driedfabric is a bright greenish yellow of excellent fastness properties.

The invention has been described in considerable detail with particularreference to certain preferred embodiments thereof, but it will beunderstood that variations and modifications can be effected within thespirit and scope of the invention as described hereinabove and asdefined in the appended claims.

What we claim is:

1. A quaternary methine compound having the formula Q=an N-pyridiniumradical or an N-quinolinium radical, R=lower alkyl, R =a p-phenyleneradical, X=a member of the class consisting of cyano,

3,247,2 1 9 '10 wherein: 9. A quaternary methine compound having theformula R:a lower alkyl radical, R R R each=lower alkyl,

4=P-P Y 5 c fi-Omorn ON Y=lower alkylene, y CHC Z- Z=an acid anion.

CH CH CH CH 4. A quaternary methine compound having the formula 3 2 2 2ON ON wherein Z- represents an acid anion.

10. A quaternary methine compound having the for- CONE: mula wherein:

Py=an N-pyridinium radical, R=lower alkyl, Y=lower alkylene, Z: an acidanion. /N OHZCEZ 5. A quaternary methine compound having the formulaCHZC Z R C CHaC 2 ON I N CH: PyYNR -CH=C z COOCH wherein 2- representsan acid anion. wherein: r 11. A compound having the formula of claim 6wherepyzan N pyridinium radical, in Z represents the ion QSO CH Rzloweralkyl, 12. A compound having the formula of claim 7 wherein Z representsthe ion OSO CH 13. A compound having the formula of claim 8 wherein Zrepresents the chloride ion. 6. A quaternary methine compound having theformula 14. A compound having the formula of claim 9 Where Y=loweralkylene, Z=an acid anion.

04119 in Z represents the chloride ion. 15. A compound having theformula of claim 10 Where- C2115) 2NCHzCHzN-CH C\ Z- in Z represents theiodide ion.

(3113 CN References (Iited by the Examiner wherein Z- represents an acidanion. UNITED STATES PATENTS 7. A quaternary methine compound having theformula 2,914,551 11/1959 Kartinos et 5 c2115 ON 3,141,018 7/1964Straley et al. 260247.2 0nnnr-orno1naq-on=o z- FOREIGN PATENTS 5H3 ON1,103,485 3/1961 Germany. wherein 2- represents an acid anion. 615,4141/1959 Italy- 8. A quaternary methine compound having the formula OTHERREFERENCES 1 lOHzOHz ON 582,316, Belgium abstracted in Derwent BelgiumCHZC/ Patents Reports, vol. 61A, page A4 (January 31, 1960).

CHsCfifl (l3H3 ON JOHN D. RANDOLPH, Acting Primary Examiner.

wherein Z represents an acid anion. WALTER MODANCE Examine

1. A QUATERNARY METHINE COMPOUND HAVING THE FORMULA